Vat dyestuffs of the acridine series



Patented Feb. 16, 1932 PATENT OFFICE HUGO WOLFE, F MANNI-IEIM, AND nnnsr nononn, on rRAnKF-onm-oN-THE-MAIN- FECHENHEIM, GERMANY, ASSIGNORS 'IO GENERAL YORK/N. Y., A. CORPORATION OF DELAWARE ANILINE' WORKS, INQ, OF NEW VAT nYEs'rUF'Fs 0]!" THE ACRIDINE SERIES N0 Drawing. Application filed Apr-i121, 193p, Serial No. 446,181, and in German mini 29, 1929.

The present invention relates to the production of vat dyestuffs of the benzanthrone series.

We have found that those anthraquinonylaminobenzanthrones' which contain several anthraquinonylamino r'adicles in the molecule and of which one is connected in its 1-pos'iti'on to the Bzl-position of the benzanthrone nucleus are converted into valuable va-t dyestuffs by treatment with alkaline condensing agents. Caustic alkalies, diluted, if desired, with organic solvents, or the alkali metal compounds of aniline and the like, or the other known alkaline condensing agents may 5 be employed for the purpose of the present invention. The products thus obtained probably correspond to the following formula:

in which at least one further aminoanthraquinonyl radicle is attached tothe benzanthrone nucleus, and in which the benz'anthrone and the aminoanthraquinonyl radi cles may be further substituted. These dyestuffs usually dissolve in concentrated sulphuric acid to give green solutions and give from olive to brown dyeingson cotton. The dyestuffs thus obtained may if desired still be subjected to a subsequent treatment with acid lcondensing agents, theshades of the dyestu-fls being changed by the said treatment. The usual acid condensing agents may be used, for example sulphuric acid or aluminium chloride to which alkali metal chlorides may be added.

The following examples will further'illustrate the nature of this invention but the in-' vention is not restricted to" these examples. The parts are by weight.

- Example 1 10 parts of di-(1 -anthraquinonyl)"-6:Bzldiaminobenzanthrone (obtainable by condensation of 1 molecular proportion of 6.321- dihalogenbenzanthrone with 2 molecular proportions of l-amino-anthraquinone) are slowly introduced while stirring at from 180 to 200 G. into a melt of 40 parts of caustic potash and from to parts of alcohol and the whole is fused at this temperature until the formation of the dyestufi is complete. The cooled melt is boiled up with water, filtered and washed. The dyestufi thus obtained is a dark paste drying to a dark powder which dissolves in concentrated sulphuric acid giving'a green coloration. The

dyestuif gives a grey brown colored vat with caustic soda solution and hydrosulphite,

from which vegetable fibres are dyed in olive brown shades.

Example 5 parts of the dyestuff obtained according to Example 1 are dissolved in 5 parts of concentrated sulphuric acid and are heated at from about 80 to 1 00 C. until the original green coloration of the solution has changed. to blue, which is the case in a shorter or longer period of time according to the strength of the sulphuric acid. The melt is then poured into water when the dyestuif separates as a flocculent green precipitate. The dyes'tuff isfiltered, washed with hot water and brought into' the form of paste. The dyestufi is a green black paste which when dried is a dark powder which dissolves in concentrated sulphuric" acid giving a blue coloration. The dyestutf gives a blue Vat Example 3 10 parts of the condensation product from 1 molecular proportion of 6.Bzldihalogenbenzanthrone with 2 molecular proportions of 1.6-diaminoanthraquinone are introduced at about 160 G. into a melt of 10 parts of caustic potash and from 20 to parts of methyl alcohol and are fused until unchanged initial material can no longer be detected. The dyestutf' Worked up in the usual manner is a dark paste which dyes Vegetable fibres olive brown shades from a grey brown colored vat. When dry the dyestufl' is a dark powder which dissolves in concentrated sulphuric acid giving a green coloration which changes to blue when the solution is heated.

Example 4 10 parts of di-(1'-anthraquinonyl) -7-Bzldiaminobenzanthrone (obtainable by condensation of 1 molecular proportion of Bzlbromo-7-chlorbenzanthrone with 2 molecular proportions of l-aminoanthraquinone) are fused as described in Example 3. After the usual working up of the melt, the dyestuil is obtained in the form of a dark colored paste which gives a brown vat with caustic soda solution and hydrosulphite from which the vegetable fibres are dyed in dark brown shades. The dyestuft dissolves in concentrated sulphuric acid giving a green coloration which changes to red brown when the solution is heated.

Ewample 5 ness to bucking.

Example 6 parts of the condensation product obtainable from 1 molecular proportion of 6- Bzl-dibromobenzanthrone and 2 molecular proportions of 1-aminol-anilido-anthraquinone, are slowly introduced into a melt of 150 parts of caustic potash and parts of ethyl alcohol kept at 160 to 170 C. The reaction temperature is then slowly raised during 1 hour to between 190 and 200 C. The cooled melt is taken up with water and the dyestuif recovered in the usual manner. It dissolves in concentrated sulphuric acid to give an olive solution and dyes cotton fast olive grey shades from a brownish black vat.

Example '7 10 parts of the dyestufi' prepared according to the foregoing example are slowly introduced into a melt of 50 parts of aluminium chloride and 10 parts of sodium chloride kept at 150 C. The temperature is then slowly raised to 160 C. and kept thereat for 2 hours. The reaction mixture is decomposed after cooling by means of water and dilute hydrochloric acid. a The dy'estufi recovered in the usual manner dissolves in concentrated sulphuric acid to give a dark brown solution and dyes cotton from a violet black vat shades similar to those obtained with the initial ma terial.

' Example 8 20 parts of the condensation product obtainable from 1 molecular proportion of 6.Bzldibr0mobenzanthrone and 2 molecular proportions of 1-amino-5-benzoylaminoanthraquinone are introduced at 150 G. into a suspension. of 90 parts of sodium anilide in 310 parts of anhydrous aniline, while passing nitrogen through the suspension. The reaction mixture is stirred at the said temperature untilthe formation of the dyestufi is com plete, whereupon the reaction mixture is allowed to cool, poured into an excess of dilute hydrochloric acid, the precipitate filtered ofi and washed with water. The dyestuff is thus obtained in the form of a dark colored paste which dyes cotton from a grey blue vat olive brown shades. The dyestufl' is a dark powder when dried, dissolving in concentrated sulphuric acid to give a green solution changing to green blue on standing.

If a condensation product obtainable from 1 molecular proportion of 6.Bzl-dibromobenzanthrone and 2 molecular proportions of 1-amino-t-benzoylaminoanthraquinone, or 1 molecular proportion each of 1-amino-5- benzoylaminoanthraquinone and l-aminoanthraquinone or another aminoanthraquinone derivative, be condensed in the aforedescribed manner dyestuffs of similar properties are obtained.

i What we claim is '1. A process of producing vat dyestufl's which comprises treating abenzanthrone substituted by several anthraquinonylamino radicles of which one is connected in its 1- position to the Bzl-position of the benzanthrone with an alkaline condensing agent.

2 A process of producing vat dyestufis whlch comprises treating a benzanthrone substituted by several anthraquinonylamino radicles of which one' is connected in its 1- position to the Bzl-position of the benzanthrone with an alkaline condensing agent 1 and subjecting the condensation product thus produced to further condensation by means of an acid condensing agent.

3. As new articles of manufacture vat dyestufis having probably the following general structure in which at least one further aminoanthraquinonyl radicle is attached to the benzan throne nucleus, the said dyestufis usually dissolving in concentrated sulphuric acid to give green solutions and dyeing cotton from olive to brown shades.

4. As a new article of manufacture the vat dyestulf probably corresponding to the formula:

the said dyestufi dissolving in concentrated sulphuric acid to give a green solution and dyeing cotton from a grey brown vat olive brown shades.

In testimony whereof we have hereunto set our hands.

- HUGO WOLFF.

ERNST HONOLD. 

